Stable, high solids methylated urea-formaldehyde coating compositions

ABSTRACT

Solutions composed of a mixture of syrupy thermosetting methylated urea-formaldehyde resins (urea:formaldehyde: methanol molar ratio 1 : 2-3 : 1-2.5; molecular size predominantly monomer to trimer) and 20 - 90% by weight of a C3-C18 polyhydric compound having a molecular weight less than about 500 are fluid and stable, and provide coatings of superior properties when they are applied as lacquers, enamels etc. to a wood or metal surface and thermoset thereon.

United States Patent [191 Blank Sept. 23, 1975 STABLE, HIGH SOLIDS METHYLATED 2,615,003 /1952 Suen ct al. 260/314 UREA FORMALDEHYDE COATING 2,995,541 8/1961 Kropa et al. 260/A X 3,247,149 4/1966 Alek 260/334 R X COMPOSITIONS Inventor: Werner Josef Blank, Wilton, Conn.

Assignee: American Cyanamid Company,

Stamford, Conn.

Filed: June 10, 1974 Appl. No.: 482,397

Related [1.8. Application Data Continuation-impart of Ser. Nos. 222,322, Jan. 31, 1972, abandoned, and Ser. No. 407,118, Oct. 17, 1973, abandoned.

US. Cl. 260/33.4 R; 260/31.2 N Int. Cl. C08K 5/10 Field of Search 260/334 R, 31.2 N

References Cited UNITED STATES PATENTS 8/1943 West 260/70 A X Primary Examiner-Lewis T. Jacobs Attorney, Agent, or Firm-Evans Kahn [57] ABSTRACT Solutions composed of a mixture of syrupy thermosetting methylated urea-formaldehyde resins (ureazformaldehyde: methanol molar ratio 1 2-3 12.5; molecular size predominantly monomer to trimer) and 20 by weight of a C -C polyhydric compound having a molecular weight less than about 500 are fluid and stable, and provide coatings of superior properties when they are applied as lacquers, enamels etc. to a wood or metal surface and thermoset thereon.

10 Claims, No Drawings STABLE, HIGH SOLIDS METHYLATED UREA-FORMALDEHYDE COATING COMPOSITIONS This is a continuation-impart of my copending applications Ser. Nos. 222,322 and 407,1 l8 filed on Jan. 3 l 1972, and Oct. 17, 1973, and both now abandoned.

The present invention relates to novel solutions substantially composed of mixtures of thermosetting methylated urea-formaldehyde resins and branched chain polyhydric C -C COmPOLh ds, both of low molecular size; to surface coatings having a content of these solutions; and to solid shaped substrate surfaces coated with the solutions in thermoset state.

It is known that thermosetting methylated liquid urea-formaldehyde resins can be employed to coat wood and metallic substrates. Unfortunately, such resins are applied as low solids solutions containing not more than about 70% solids because solutions of higher solids content are too viscous to be applied by most industrially practical means. Moreover, when solutions of from 80 to 100% of such methylated urea-formaldehyde resins and O to 20% of a straight-chain polyfunctional alcohol are applied to surfaces and are thermoset thereon, the resulting coatings are frequently unsatisfactory owing to the tendency of the solutions to form imperfect films. The solutions crawl and leave craters while they are being heated to thermosetting temperatures, and the resulting coatings possess poor chemical and physical properties, having poor resistance to common organic solvents and being unduly either hard and brittle, or sticky, soft, and rubbery. A composition which would provide coatings free of these shortcomings would fulfill a long-felt need in the art.

The solutions of the present invention consist essentially of (A) 80 to 10% by weight of a mixture of a thermosetting methylated urea-formaldehyde condensate in 1 2-3 l2.5 urea: formaldehyde-methanol molar ratio, 10 to 60% of said condensate by weight. being in monomeric state, 10 to 75% thereof being in dimeric state, 5 to 60% thereof being in trimeric state, and to 30% thereof being in higher than trimeric state, said percentages totalling 100%; and (B) to 90% by weight of one or more branched chain polyhydric compounds containing 3 to 18 carbon atoms and having a molecular weight less than 500. The composition thus is of very low average molecular weight.

As a result of the requirement that the urea condensate be predominantly in the monomeric-trimeric range and that it have a content of at least three of the aforesaid mer forms, the above-described solutions in preferred instances possess the following beneficial properties.

l. The solutions have a low viscosity. As a result, they can be sprayed at 100% solids. No diluent or thinner is required, thus eliminating a fire hazard and need for a solvent recovery system.

2. The solutions are compatible with known thickeners, and so can be rendered suitable for application by brush, knife, or roll.

3. The solutions possess adequate stability. They thus can be shipped at 100% solids even when containing a condensation catalyst and need not contain inhibitors or stabilizers. The solutions thus may be used as shipped, and the user need not perform any mixing step.

4. The solutions are soluble in water and in 3 l butanol-toluene mixture. They can thus be thinned with water, and can be used as components of spirit soluble varnishes and enamels. Equipment containing the solutions can be readily cleaned with water or with an organic solvent.

5. When thermocured, coatings of the solutions possess excellent flexibility and resistance to harm by so]- vents. As a result, the solutions can be used to provide coatings on sheet metal or wood intended for contact with organic solvents.

The branchings in the chains of the polyhydric compound preventthe solutions of the present invention from crawling or forming pinholes and craters on the surfaces to which they have been applied while the coatings are being heated to temperatures at which they thennosetfAs a result, the surfaces are uniformly and completely coated, and pieces lacquered or enamelled with th'esolutions are generally passed on inspection as satisfactory.

The solutions of the present invention can contain any of the materials which are now customarily present in methylated urea-formaldehyde coating compositions. Thus they may contain viscosity flow modifiers (generally termed thickening agents or anti-sag agents) of the polyester, polyether or acrylic resin types, generally in amount from 5 to 20% of the overall composition. If further desired the solutions can contain a volatile aqueous or organic solvent as diluent or thinner to gether with a non-volatile thickening agent. The viscosity of the resulting composition is low, but the viscosity increases after the coating has been sprayed (because of evaporation of solvent). By this means a comparati ely viscous coating can be applied which possesses less tendency to sag on vertical surfaces. Suitable diluents include water, ethanol and 3 l butanol 2 toluene, and a variety of anti-sag agents are known in the art. The solutions can also contain dyes and pigments and acid catalysts.

An important property of the solutions of the present invention is that they are extremely fluid at high solids content. As a result, the solutions of the present invention can be applied by knife coater, by brush or by roller coater even at solids, and can be applied by spray when thinned, to any desired shaped solid surface. It is an extraordinary feature of the invention that in preferred instances the solutions, when prepared, are usually too thin to be sprayed satisfactorily on vertical surfaces. In such instances the solutions can be rendered suitable for spraying by addition of a non-volatile thickener, as described above.

The aforesaid urea formaldehyde methanol molar ratio range of l 23 12.5 is critical for the composition of the urea-formaldehyde-methanol condensate, for the following reasons.

When the amount of reacted formaldehyde is less than about two mols per mol of reacted urea, the condensate thermosets comparatively slowly and produces films which are unacceptably soft. Three mols of formaldehyde is the virtual maximum which it is possible to react. The range of 23 represents the maximum amount of formaldehyde which it is practical to react, and so represents the preferred range.

With regard to methanol, when the amount of reacted methanol is less than one mol per mol of urea, the resulting condensate tends to have poor compatability with the added polyhydric compound, so that thermosetting is undesirably slow and the films obtained are comparatively weak. The value of 2.5 mols represents the largest amount which provides good compatability with the polyhydric compound, fast 'thermosetting properties, and comparatively strong films.

the invention, and the claims are not to be construed as 1 limited thereto.

1 ,G-Hexanediol The solutions can be formulated into lacquerand enamel-type coating compositions by addition thereto EXAMPLE 1 of known dyes and pigments; plasticizers; ultra-violet This example illustrates the preparation of a methylabsorptive compounds; insecticides; supplementary ated urea-formaldehyde resin which can be employed coating compositions including oxidizing type alkyd as a component of the coating solution of the present resins; the solvent thickening agent compositions deinvention. scribed above; and curing catalysts. To a two-liter, three-necked flask equipped with stir- Methylated urea-formaldehyde resins suitable for rer, condenser, and thennometer are charged 288 parts formulation of solutions of the present invention are of methanol, 297 parts of 91% paraformaldehyde, and disclosed in US. Pat. applications Ser. Nos. 216,257 triethanolamine to adjust the pH to 9 to 10. The temand 216,258 filed on Jan. 7, 1972, by Leonard J. Calbo, perature is raised to 50C. and 180 parts of urea are Jr. now abandoned which also disclose methods for added over a period of twenty minutes. The mixture is their preparation. The condensation products of which heated to reflux (81C.). Refluxing is continued for 25 these syrups are composed are about 30% monomeric to 30 minutes or until the mixture is clear and homogeby weight, 50% dimeric and trimeric. neous. The mixture is cooled to 75C. and to it is added According to one method, the urea condensate can 20 over seven minutes (to prevent excessive exotherm) be prepared by refluxing in the anhydrous state a urea, sufficient 90% aqueous formic acid to decrease the pH formaldehyde, and methanol at a pH of at least 8 to efof the mixture to 4.5 5.5. The mixture is then brought feet urea-formaldehyde reaction, continuing the reacto reflux (about 84C.), and refluxing is continued for tion at a pH between 4.5 and 5.5, lowering the pH to about 3 hours. At the end of this period, the rate of refrom 2 to 3 and continuing the reaction for about one action of the methanol with the urea-formaldehyde rehour until a syrupy, low polymeric material has been action product has become slow. obtained, not more than about a third of which has a The mixture is thenv allowed to cool to 25C., and molecular size larger than trimeric. 70% aqueous nitric acid is uniformly added over seven Exemplary of polyhydric branched-chain compounds minutes to adjust the pH downward to 2 3. The mixwhich contain at least 3 and preferably from 6 to 18 ture is then stirred at 25 to 30C. until a urea-forcarbon atoms or more, are: trimethylol ethane, trimethmaldehyde-methanol polymer is formed. About one ylol lpropane, 1,2-propylene glycol, 2-ethyll ,3-hexhour is generally required. The mixture is then adjusted anediol, neopentyl glycol, trimethyl pentane diol, and to pH 7 to 8 with 50% aqueous sodium hydroxide soluhydroxypivalyl hydroxypivalate. Preferably the polytion and stripped under reduced pressure to remove hydric compounds have molecular weights less than 5 substantially all of the volatiles present (water, formalabout 500. When the compounds have higher molecu- ,dehyde, and methanol). The terminal temperature of lar weights, a volatile solvent material is generally rethe stripping step is about 100C. The resultant syrup is quired to effect compatibility as a result of whichthe cooled to room temperature. It is composed of interresolids content of the solution must be below 80%. acted urea, formaldehyde and methanol in l 2.4.: 1.6 Moreover, mixtures of, for-instance, equal parts by molar ratio, and is watersoluble. Two thirds or less is in weight of (a) the latter polyhydric compound and (b) a trimeric or lower state.

branched-chain monoh dric alcohol, such as isodecanol or isooctadecangl, can, if desired, be employed EXAMPLES 2 to 13 in preparing the solutions of the present invention. These examples illustrate the preparation and prop- These polyols are substantially non-volatile at thermoerties of a variety of solutions of the urea resin of Exsetting temperatures. ample l, a branched chain C C polyhydric com-' The urea condensate branched chain polyhydric pound having a molecular weight below 500, and (or, compound need not contain a catalyst, particularly if for the sake of comparison, some other alcohol), opthe composition is to be cured at high temperature. tionally, an acid catalyst. The compositions of the solu- However, if a thermosetting, or curing temperature tions are shown in the table below, together with the of less than about 150C. is to be utilized, an acidic specific polyhydric compound or other alcohol empolycondensation catalyst is required to obtain curing ployed. The solutions are fluid. Although containing an within a practical period of time, say between about 5 active acid catalyst, each solution has a pot life of at seconds and sixty minutes. Typical active catalysts are: least seven days, and is therefore regarded as stable. phosphoric acid, butylphosphoric acid, sulfuric acid, The solutions are poured over 4 X 12 inch stainless hyrochloric acid, methane sulfonic acid, p-toluenesulsteel panels and are allowed to drain for ten minutes. fonic acid, magnesium bromide and equivalents of the The panels are then baked or cured at 125C. for .ten same. Previously known latent catalysts can also be minutes. used, for example ammonium chloride.

TABLE I EXAMPLES COMPARATIVE COMPOSITION EXAMPLES Parts by weight 2 3 4 5 6 7 8 9 l0 l1 l2 l3 Urea Resin (Example 1) 8 20 '30 30 40 40 80 90 40 25 35 Hydroxypivalyl i Hydroxypivalate 92 80 35 30 60 20 10 2-Methyl-2,4-Pentanediol 35 30 1,5-Pentanediol 60 40 g I;

TABLE l-continued EXAMPLES COMPARATIVE COMPOSITION EXAMPLES Parts by weight 2 3 4 5 6 7 8 9 l0 1 1 l2 l3 p-Toluol Sulfonic Acid 1.5 1.5 1.5 1.5 1.5 1.5 1.5 3 3 3 3 Aqueous Solution) I Ethanol l0 Knoop Hardness. Sticky 0.5%6 "3.5 4 7 6 1 Soft 26 7 10 20 (Tukon Hardness) It will be noted that, with the exception of Examples tough, mar resistant and smooth films which are free from craters and pinholes. The films resist acetone and other solvents.

It will be further noted that the films of Examples 10 to 13 are hard. However, the appearance of thermoset.

coating is extremely poor with a preponderance of craters on the surface and bad crawling of the coating from the corners and edges. The films are non-uniform in thickness and do not render the surface satisfactory with respect to chemical or physical protection of the substrate. Significantly, nonbranched-chain polyhydric aliphatic alcohols do not impart the desired attributes to the substrates so-coated.

Simlar films are obtained when trimethylol ethane is employed in lieu of hydroxypivalyl hydroxypivalate. When omitting the acid catalyst in each of the examples, similar films are obtained when baking or curing to a temperature of 175C. instead of a temperature of 125C.

EXAMPLES 14 to 17 Several solutions of urea resin as above-defined, dipropylene glycol,

and acid catalyst are utilized as in Examples 2 to 13 above. The compositions and hardness results of the cured films are summarized in Table 11 below.

A solution of the following components is prepared by admixing 50 parts of urea resin (Example 1), 50 parts of dipropylene glycol, 90 parts of rutile titanium dioxide, and 3 parts of p-toluenesulfonic acid (20% so-. lution). The mixture of above components is ground on a three roll mill. The viscous solution is drawn on aluminum panels and baked for ten minutes at 125 C. The resulting film has a very high glossand a pencil hardness of H-2H. P

' EXAMPLES 19 to 21 Several solutions of urea resin, dipropylene glycol, and acid catalyst as indicated in Table III below are prepared and cast on aluminum.

(inch pounds) The wet film thickness is 2.0 mil. The coating-is baked at 100C. for ten minutes. Films drawn with the solution of Example 19, for instance, on aluminum and glass, are dry to the touch and completely cross-linked either after 16 hours at room temperature or after a baking cycle of one minute at 150C. The acid-catalyzed mixtures exhibit only slight, almost undetectible viscosity increases after seven days at room temperature.

EXAMPLE 22 This example illustrates a composition according to the present invention containing an acrylic resin as non-volatile viscosity modifier and ethanol as volatile diluent. The acrylic resin is a copolymer of butyl acrylate, styrene, and hydroxypropyl maleate (50/30/20) dissolved in n-butanol.

A solution is prepared of parts of urea resin (Example l), 80 parts of dipropylene glycol, 54 parts of acrylic resin (75% solution). 180 parts of rutile titanium dioxide, 1.0 part of diisopropanolamine, and 4 parts of p-toluenesulfonic acid (20% solution in isopropanel). The resulting composition is of brushable viscosity. To this is added 25 parts of ethanol (96%) as volatile diluent.

The above components are mixed in a ball mill. The resultant solids composition is of sprayable viscosity and has a viscosity of 35" Ford 4 Cup. Aluminum panels are next sprayed and baked ten minutes at C. and have a good appearance and a pencil hardness of 31-1-4H. The composition sprays readily and the I applied coating does not sag.

EXAMPLE 23 The procedure of Example 18 is repeated except that the solution is thinned to brushable viscosity by addition of a small quantity of water. The resulting solution provides clear, glossy hard coatings when applied to' primed steel panels and to hardwood veneer and thermoset.

I claim:

1. A solution consisting essentially of (A) 80% to by weight of a syrupy mixture of thermosetting methylated urea-formaldehyde condensates composed of inter-reacted urea, formaldehyde and methanol in 1 2-3 l2.5 molar ratio respectively, wherein 10 to 60% by weight of said mixture is monomeric, 10 to 75% by weight is dimeric, 5 to 60% by weight is trimeric; and 10 to 30% by weight is in excess of trimeric, said percentages totalling 100; and (B) to 90% by weight of a branched-chain C -C polyhydric compound having a molecular weight less than 500.

2. A solution according to claim 1 wherein the ratio of inter-reacted urea, formaldehyde and methanol in the condensate is 1 2.2.4 1.6. v

3. A solution according to claim 1 containing a small but effective amount of an acid poly condensation catalyst. I

4. A solution according to claim 3 wherein the catalyst is p-toluenesulfonic acid.

5. A solution according to claim 1 wherein the weigh of the polyhydric cross-linking agent is /2 to the hydric compound is trimethylol ethane. 

1. A SOLUTION CONSISTING ESSENTIALLY OF (A) 80% TO 10% BY WEIGHT OF A SYRUPY MIXTURE OF THERMOSETTING METHYLATED UREAFORMALDEHYDE CONDENSATES COMPOSED OF INTER-REACTED UREA, FORMALDEHYDE AND METHANOL IN 1:2-3:1-2.5 MOLAR RATIO RESPECTIVELY, WHEREIN 10 TO 60% BY WEIGHT OF SAID MIXTURE IS MONOMERIC, 10 TO 75% BY WEIGHT IS DIMETRIC, 5 TO 60% BY WEIGHT IS TRIMERIC, AND 10 30% BY WEIGHT IS IN EXCESS OF TRIMERIC, SAID PERCENTAGES TOTALLING 100, AND (B) 20 TO 90% BY WEIGHT OF A BRANCHED-CHAIN C3-C18 POLYHYDRIC COMPOUND HAVING A MOLECULAR WEIGHT LESS THAN
 500. 2. A solution according to claim 1 wherein the ratio of inter-reacted urea, formaldehyde and methanol in the condensate is 1 : 2.4 : 1.6.
 3. A solution according to claim 1 containing a small but effective amount of an acid poly condensation catalyst.
 4. A solution according to claim 3 wherein the catalyst is p-toluenesulfonic acid.
 5. A solution according to claim 1 wherein the weight of the polyhydric cross-linking agent is 1/2 to 2/3 the weight of the urea-formaldehyde condensate.
 6. A solution according to claim 1 containing 10% by weight of ethanol.
 7. A solution according to claim 1 wherein the polyhydric compound is hydroxypivalyl hydroxypivalate.
 8. A solution according to claim 1 wherein the polyfunctional alcoholic reactant is trimethylol propane.
 9. A solution according to claim 1 in which the polyhydric compound is a 50 : 50 mixture of 2-methyl-2,4-pentanediol and hydroxypivalyl hydroxypivalate, respectively.
 10. A solution according to claim 1 in which the polyhydric compound is trimethylol ethane. 